JP7280146B2 - Polyamide composition, method for producing the same, and molded article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyamide composition, a method for producing the same, and a molded article.

Compositions based on aliphatic polyamides have an excellent profile of properties and are therefore used for producing moldings in a great many applications. Polyamide compositions with flame retardant properties are required especially for components in the electrical and electronic industry to ensure adequate fire protection.

Polyamides are often flame-retardant treated by the addition of halogen compounds. Recently, however, various regulations prohibiting the use of products containing halogen compounds in electrical and electronic parts due to hazardous substance regulations such as RoHS (Restriction of Hazardous Substances) and PoHS (Prohibition on Certain Hazardous Substances in Consumer Products). is defined. For this reason, several non-halogen flame retardants have been developed for polyamides.

Non-halogen flame retardants include, for example, phosphorus compounds. US Pat. No. 6,300,001 discloses the use of calcium and aluminum salts of phosphinic or diphosphinic acids as flame retardants for polyamides. Specimens with a thickness of 1.2 mm, manufactured from a polyamide composition containing these non-halogen flame retardants and reinforced with 30% by weight of glass fibers relative to the total weight of the composition, had a flammability classification of V- according to UL94. achieve 0.

In Patent Document 2, in order to achieve UL94 flammability classification V-0, in a glass fiber reinforced polyamide composition containing polyamide 6 as a main component, 20% by mass of the total mass of the composition is far It is disclosed that greater than 30% by weight of aluminum phosphinate is required in glass fiber reinforced polyamide compositions based on polyamide 66. US Pat. Thus, when using a phosphinic acid-based flame retardant, a large amount must be added in order to achieve the flammability classification V-0, which poses a problem of adversely affecting mechanical properties.

Thus, US Pat. No. 6,200,009 discloses a polyamide composition based on a mixture of an aliphatic polyamide and a semi-aromatic polyamide containing phosphinates as flame retardants. It has been reported that the addition of semi-aromatic polyamide can reduce the amount of flame retardant used and improve tensile elongation.

Further, Patent Document 4 discloses a polyamide composition based on a mixture of a polyamide containing an aromatic polyamide and a polyphenylene sulfide, using a phosphinate as a flame retardant. It has been reported that by adding polyphenylene sulfide, which has excellent flame retardancy, to a polyamide containing an aromatic polyamide, the amount of flame retardant used can be reduced, and the amount of outgassing derived from the flame retardant can be reduced.

Japanese Patent No. 3947261 Japanese Patent No. 4698789 Japanese Patent No. 4614959 JP 2009-270107 A JP 2005-179362 A EP-A-699708 JP-A-08-073720

However, although the polyamide composition described in Patent Document 3 has improved tensile elongation at break by reducing the amount of flame retardant used, the bending elastic modulus under atmospheric equilibrium moisture absorption required for automobiles and various electrical parts , there is room for improvement in terms of long-term heat resistance and the like.
In addition, the polyamide composition described in Patent Document 4 reduces the amount of flame retardant used by adding polyphenylene sulfide and reduces outgassing, but when the ratio of aliphatic polyamide to aromatic polyamide is increased, There is a problem that it becomes difficult to maintain the flammability classification V-0 according to UL94. Another concern is the deterioration of the CTI (Comparative Tracking Index), which is required especially for electrical parts.
As described above, in the prior art, a halogen-free polyamide composition having excellent flame retardancy, tensile strength, flexural modulus upon water absorption, and long-term heat resistance is not yet known.

The present invention has been made in view of the above circumstances, and a polyamide composition having excellent flame retardancy and good long-term heat resistance when formed into a molded article despite not containing halogen, and a method for producing the same. and a molded article comprising said polyamide composition.

That is, the present invention includes the following aspects.
The polyamide composition according to the first aspect of the present invention is
(A) an aliphatic polyamide;
(B) a semi-aromatic polyamide containing diamine units and dicarboxylic acid units;
(C) at least one phosphinate selected from the group consisting of a phosphinate represented by the following general formula (1), a diphosphinate represented by the following general formula (2), and condensates thereof; ,
(D) a polymer having an oxygen index of 27% or more and having an aromatic group in its main chain;
A polyamide composition containing
The (B) semi-aromatic polyamide contains 50 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semi-aromatic polyamide,
The content of the (D) polymer is 0.1% by mass with respect to the total mass of the (A) aliphatic polyamide, the (B) semi-aromatic polyamide, the (C) phosphinates and the (D) polymer It is more than 8 mass % or less.

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M ⁿ¹¹⁺ is an n11-valent metal ion. M is calcium or aluminum , n11 is 2 or 3. When n11 is 2 or 3, a plurality of R ¹¹ and R ¹² may be the same or different.
In general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M′ ^m21+ is an m21 valent metal ion. M' is calcium or aluminum . n21 is an integer of 1 or more and 3 or less. When n21 is 2 or 3, multiple R ²¹ , R ²² and Y ²¹ may be the same or different. m21 is 2 or 3; x is 1 or 2; When x is 2, multiple M' may be the same or different. n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x. )

The (D) polymer may be polyphenylene sulfide, polyphenylene ether, or maleic anhydride-modified polyphenylene ether.
The (A) aliphatic polyamide may contain a diamine unit and a dicarboxylic acid unit.
The (A) aliphatic polyamide may be polyamide 66.

The content of the (C) phosphinates is 0 with respect to the total mass of the (A) aliphatic polyamide, the (B) semi-aromatic polyamide, the (C) phosphinates and the (D) polymer .1 mass % or more and 30 mass % or less may be sufficient.
A tan δ peak temperature of the polyamide composition may be 90° C. or higher.
The content of (B) the semi-aromatic polyamide in the polyamide composition may be 5% by mass or more and 50% by mass or less with respect to the total mass of the polyamide in the polyamide composition.
The (B) semi-aromatic polyamide may contain 75 mol % or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semi-aromatic polyamide.
The (B) semi-aromatic polyamide may contain 100 mol % of isophthalic acid units in all the dicarboxylic acid units constituting the (B) semi-aromatic polyamide.
The weight average molecular weight of the polyamide composition may be 10,000 or more and 50,000 or less.
The polyamide composition according to the first aspect may further comprise at least one (E) filler.

A molded article according to the second aspect of the present invention is obtained by molding the polyamide composition according to the first aspect.

A method for producing a polyamide composition according to a third aspect of the present invention is a method for producing the polyamide composition according to the first aspect, comprising: the (A) aliphatic polyamide; the (B) semi-aromatic polyamide; It is a method of melt-kneading raw material components containing the (C) phosphinate and the (D) polymer.

According to the polyamide composition of the above aspect and the method for producing the same, a molded article having excellent flame retardancy and good long-term heat resistance can be obtained in spite of containing no halogen. The molded article of the above embodiment does not contain halogen, and despite not containing halogen, it has excellent flame retardancy and good long-term heat resistance.

EMBODIMENT OF THE INVENTION Hereinafter, the form (only henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

As used herein, the term "polyamide" means a polymer having an amide (--NHCO--) group in its main chain.

<<Polyamide composition>>
The polyamide composition of this embodiment contains the following components (A) to (D).
(A) an aliphatic polyamide;
(B) a semi-aromatic polyamide containing diamine units and dicarboxylic acid units;
(C) phosphinates;
(D) A polymer having an oxygen index of 27% or more and having an aromatic group in the main chain (hereinafter sometimes simply abbreviated as "(D) polymer")

In the polyamide composition of the present embodiment, the content of component (D) with respect to the total mass of components (A) to (D) is 0.1% by mass or more and 8.0% by mass or less.

The (C) phosphinates are phosphinates represented by the following general formula (1) (hereinafter sometimes abbreviated as "phosphinate (1)") and represented by the following general formula (2): diphosphinate (hereinafter sometimes abbreviated as "diphosphinate (2)") and at least one phosphinate selected from the group consisting of condensates thereof.

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M ⁿ¹¹⁺ is an n11-valent metal ion M is an element or transition element belonging to Group 2 or Group 15 of the periodic table, n11 is 2 or 3. When n11 is 2 or 3, the plurality of ^R11 and ^R12 are each They may be the same or different.
In general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M′ ^m21+ is an m21 valent metal ion. M' is an element belonging to group 2 or group 15 of the periodic table or a transition element. n21 is an integer of 1 or more and 3 or less. When n21 is 2 or 3, multiple R ²¹ , R ²² and Y ²¹ may be the same or different. m21 is 2 or 3; x is 1 or 2; When x is 2, multiple M' may be the same or different. n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x. )

The polyamide composition of the present embodiment, which has the above structure, does not contain halogen, is excellent in flame retardancy, and provides a molded article having excellent tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

<Characteristics of Polyamide Composition>
The molecular weight and tan δ peak temperature of the polyamide composition of the present embodiment can be configured as follows, and specifically, can be measured by the methods described in the examples below.

[Weight average molecule (Mw) of polyamide composition]
A weight average molecular weight (Mw) can be used as an index of the molecular weight of the polyamide composition.
The weight average molecule (Mw) of the polyamide composition is preferably 10000 or more and 50000 or less, more preferably 17000 or more and 45000 or less, more preferably 20000 or more and 45000 or less, even more preferably 25000 or more and 45000 or less, and particularly preferably 30000 or more and 42000 or less. , 35000 or more and 40000 or less.
When the weight average molecular weight (Mw) of the polyamide composition is within the above range, a polyamide composition having excellent mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, etc., can be obtained. In addition, the molded article obtained from the polyamide composition containing the component represented by (E) the filler is excellent in tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

As a method for controlling the Mw of the polyamide composition within the above range, for example, (A) an aliphatic polyamide, (B) a semi-aromatic polyamide, and (D) a polymer having a Mw within the range described later can be used. are mentioned.
In addition, Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in Examples below.

[tan δ peak temperature of polyamide composition]
The lower limit of the tan δ peak temperature of the polyamide composition is preferably 90°C, more preferably 105°C, and even more preferably 110°C.
On the other hand, the upper limit of the tan δ peak temperature of the polyamide composition is preferably 150°C, more preferably 140°C, and even more preferably 130°C.
That is, the tan δ peak temperature of the polyamide composition is 90° C. or higher, preferably 105° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 140° C. or lower, even more preferably 110° C. or higher and 130° C. or lower.
When the tan δ peak temperature of the polyamide composition is equal to or higher than the above lower limit, it tends to be possible to obtain a polyamide composition that is more excellent in water absorption rigidity and heat rigidity. On the other hand, since the tan δ peak temperature of the polyamide composition is equal to or less than the above upper limit, the molded article obtained from the polyamide composition containing the component represented by (E) the filler has tensile strength and bending when absorbing water. It tends to be superior in terms of elastic modulus and long-term heat resistance.

Examples of the method for controlling the tan δ peak temperature of the polyamide composition within the above range include a method for controlling the contents of (A) the aliphatic polyamide and (B) the semi-aromatic polyamide within the range described below.

Details of each constituent component of the polyamide composition of the present embodiment are described below.

<(A) Aliphatic Polyamide>
The constitutional unit of (A) the aliphatic polyamide contained in the polyamide composition of the present embodiment preferably satisfies at least one of the following conditions (1) and (2).
(1) containing (Aa) aliphatic dicarboxylic acid units and (Ab) aliphatic diamine units;
(2) containing at least one selected from the group consisting of (Ac) lactam units and aminocarboxylic acid units;
The polyamide composition of the present embodiment can contain, as (A) aliphatic polyamide, one or two or more polyamides that satisfy at least one of the above conditions (1) and (2). Above all, it is particularly preferable that the constitutional unit of (A) the aliphatic polyamide contained in the polyamide composition of the present embodiment satisfies the above (1).

[(Aa) aliphatic dicarboxylic acid unit]
(Aa) The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit includes, for example, linear or branched saturated aliphatic dicarboxylic acids having 3 or more and 20 or less carbon atoms.
Linear saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms are not limited to the following, but examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. , sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, diglycolic acid, and the like.
Examples of the branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid and the like.
The aliphatic dicarboxylic acids constituting these (Aa) aliphatic dicarboxylic acid units may be used alone or in combination of two or more.
Among them, polyamide compositions tend to have better heat resistance, fluidity, toughness, low water absorption, and rigidity. Linear saturated aliphatic dicarboxylic acids having 6 or more carbon atoms are preferred.

Specific examples of preferred linear saturated aliphatic dicarboxylic acids having 6 or more carbon atoms include adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and the like. be done.
Among them, adipic acid, sebacic acid, or dodecanedioic acid is preferable as the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms from the viewpoint of the heat resistance of the polyamide composition.

In addition, (A) the aliphatic polyamide may further contain a unit derived from a polycarboxylic acid having a valence of 3 or more, if necessary, as long as the effects of the polyamide composition of the present embodiment are not impaired. Trivalent or higher polyvalent carboxylic acids include, for example, trimellitic acid, trimesic acid, pyromellitic acid and the like. These trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.

[(Ab) aliphatic diamine unit]
(Ab) As the aliphatic diamine constituting the aliphatic diamine unit, for example, a linear saturated aliphatic diamine having 2 to 20 carbon atoms, or a branched saturated aliphatic diamine having 3 to 20 carbon atoms diamine and the like.
Examples of straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine and the like.
Examples of the branched saturated aliphatic diamine having 3 to 20 carbon atoms include, but are not limited to, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also called 2-methyloctamethylenediamine), 2,4-dimethyloctamethylene diamine and the like.
The aliphatic diamines constituting these (Ab) aliphatic diamine units may be used alone or in combination of two or more.
Among them, the number of carbon atoms in the aliphatic diamine constituting the (Ab) aliphatic diamine unit is preferably 6 or more and 12 or less, more preferably 6 or more and 10 or less. (Ab) When the number of carbon atoms in the aliphatic diamine constituting the aliphatic diamine unit is at least the above lower limit, the heat resistance of the obtained molded article is more excellent. On the other hand, when the number of carbon atoms is equal to or less than the above upper limit, the crystallinity and releasability of the resulting molded article are more excellent.

Specific examples of preferred linear or branched saturated aliphatic diamines having 6 to 12 carbon atoms include hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine, and the like. mentioned.
Among them, hexamethylenediamine or 2-methylpentamethylenediamine is preferable as the linear or branched saturated aliphatic diamine having 6 to 12 carbon atoms. By containing such (Ab) aliphatic diamine units, the heat resistance and rigidity of molded articles obtained from the polyamide composition are more excellent.

In addition, (A) the aliphatic polyamide may further contain a unit derived from a polyvalent aliphatic amine having a valence of 3 or more, if necessary, as long as the effects of the polyamide composition of the present embodiment are not impaired. Examples of trivalent or higher polyvalent aliphatic amines include bishexamethylenetriamine.

[(Ac) at least one structural unit selected from the group consisting of lactam units and aminocarboxylic acid units]
(A) The aliphatic polyamide can contain at least one structural unit selected from the group consisting of (Ac) lactam units and aminocarboxylic acid units. By containing such units, there is a tendency to obtain a polyamide having excellent toughness.
As used herein, the terms "lactam unit" and "aminocarboxylic acid unit" refer to poly(condensed) lactam and aminocarboxylic acid.

Examples of the lactam constituting the lactam unit include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprylolactam, enantholactam, undecanolactam, laurolactam (dodecanolactam), and the like. be done.
Among them, the lactam constituting the lactam unit is preferably ε-caprolactam or laurolactam, more preferably ε-caprolactam. Containing such a lactam tends to improve the toughness of molded articles obtained from the polyamide composition.

Examples of the aminocarboxylic acid constituting the aminocarboxylic acid unit include, but are not limited to, ω-aminocarboxylic acids and α,ω-amino acids, which are lactam ring-opened compounds.
The aminocarboxylic acid constituting the aminocarboxylic acid unit is preferably a straight-chain or branched-chain saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω-position. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Moreover, para-aminomethyl benzoic acid etc. are mentioned as an aminocarboxylic acid.

These (Ac) lactams and aminocarboxylic acids constituting at least one structural unit selected from the group consisting of lactam units and aminocarboxylic acid units may be used singly or in combination of two or more. may be used in combination.

Among them, the (A) aliphatic polyamide contained in the polyamide composition of the present embodiment is preferably a polyamide containing a dicarboxylic acid unit and a diamine unit from the viewpoint of mechanical properties, heat resistance, moldability and toughness. 66 (PA66) is more preferred. PA66 is considered a suitable material for automotive parts because of its excellent mechanical properties, heat resistance, formability and toughness.

The content of (A) the aliphatic polyamide in the polyamide composition of the present embodiment can be, for example, 10% by mass or more and 100% by mass or less, relative to the total mass of the polyamide in the polyamide composition. It can be from 55% by mass to 100% by mass, for example, from 55% by mass to 100% by mass.

[(A) weight average molecular weight Mw (A) of aliphatic polyamide]
(A) As an index of the molecular weight of the aliphatic polyamide, the weight average molecular weight Mw (A) can be used. The weight average molecular weight Mw (A) of the aliphatic polyamide is preferably 10000 or more and 50000 or less, more preferably 17000 or more and 45000 or less, more preferably 20000 or more and 45000 or less, even more preferably 25000 or more and 45000 or less, especially 30000 or more and 45000 or less. It is preferably 35,000 or more and 40,000 or less, most preferably.
When the weight average molecular weight Mw (A) is in the above range, mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, tensile strength when molded, bending elastic modulus when water is absorbed, and long-term A polyamide composition having excellent heat resistance and the like can be obtained.
The weight average molecular weight Mw (A) can be measured using GPC as described in the examples below.

<(B) Semi-aromatic polyamide>
The (B) semi-aromatic polyamide contained in the polyamide composition of the present embodiment is a polyamide containing diamine units and dicarboxylic acid units.
The (B) semi-aromatic polyamide preferably contains 20 mol% or more and 80 mol% or less of aromatic constitutional units, and 30 mol% or more and 70 mol% of the total constitutional units of the (B) semi-aromatic polyamide. It more preferably contains the following aromatic structural units, and more preferably contains 40 mol % or more and 60 mol % or less of aromatic structural units. The "aromatic structural unit" as used herein means an aromatic diamine unit and an aromatic dicarboxylic acid unit.

In addition, (B) the semi-aromatic polyamide includes (B-a) dicarboxylic acid units containing 50 mol% or more of isophthalic acid units with respect to the total dicarboxylic acid units of the (B) semi-aromatic polyamide, and a dicarboxylic acid unit having 4 or more carbon atoms. Polyamides containing (Bb) diamine units containing 10 or less diamine units are preferred.
Also, at this time, the total content of isophthalic acid units and diamine units having 4 to 10 carbon atoms in the (B) semi-aromatic polyamide is 50 mol with respect to all constituent units of the (B) semi-aromatic polyamide. % or more, more preferably 80 mol % or more and 100 mol % or less, even more preferably 90 mol % or more and 100 mol % or less, and particularly preferably 100 mol %.

The ratio of the predetermined monomer units constituting the (B) semi-aromatic polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.

[(Ba) dicarboxylic acid unit]
The (Ba) dicarboxylic acid unit is not particularly limited, and examples thereof include aromatic dicarboxylic acid units, aliphatic dicarboxylic acid units, and alicyclic dicarboxylic acid units.
Among them, the (Ba) dicarboxylic acid unit preferably contains 50 mol% or more of the isophthalic acid unit, and 65 mol% or more of the isophthalic acid unit , based on the total number of moles of the (Ba) dicarboxylic acid unit . It is more preferably 100 mol % or less, more preferably 75 mol % or more and 100 mol % or less, particularly preferably 80 mol % or more and 100 mol % or less, and most preferably 100 mol %.
(B-a) When the ratio of the isophthalic acid unit in the dicarboxylic acid unit is at least the above lower limit, a polyamide composition can be obtained which simultaneously satisfies mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, and the like. There is a tendency. In addition, molded articles obtained from polyamide compositions tend to be more excellent in tensile strength, flexural modulus when water is absorbed, and long-term heat resistance.

(aromatic dicarboxylic acid unit)
Examples of aromatic dicarboxylic acids constituting aromatic dicarboxylic acid units other than isophthalic acid units include, but are not limited to, dicarboxylic acids having aromatic groups such as phenyl and naphthyl groups. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.

Although the substituent is not particularly limited, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and 7 to 10 carbon atoms. alkylaryl groups, halogen groups, silyl groups having 1 to 6 carbon atoms, sulfonic acid groups and salts thereof (sodium salts, etc.).
The alkyl group having 1 to 4 carbon atoms is not limited to the following, but examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. etc.
Examples of the aryl group having 6 to 10 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group.
Examples of the arylalkyl group having 7 or more and 10 or less carbon atoms include, but are not limited to, a benzyl group.
Examples of the alkylaryl group having 7 to 10 carbon atoms include, but are not limited to, tolyl group and xylyl group.
Examples of halogen groups include, but are not limited to, fluoro, chloro, bromo, and iodo groups.
Examples of the silyl group having 1 to 6 carbon atoms include, but are not limited to, trimethylsilyl group and tert-butyldimethylsilyl group.
Among them, aromatic dicarboxylic acids constituting aromatic dicarboxylic acid units other than isophthalic acid units are preferably unsubstituted or substituted with predetermined substituents and having 8 to 20 carbon atoms.

Specific examples of aromatic dicarboxylic acids having 8 to 20 carbon atoms that are unsubstituted or substituted with a predetermined substituent include, but are not limited to, terephthalic acid, naphthalenedicarboxylic acid, 2-chloro terephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid and the like.
The aromatic dicarboxylic acids constituting the aromatic dicarboxylic acid unit may be used singly or in combination of two or more.

(aliphatic dicarboxylic acid unit)
Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include linear or branched saturated aliphatic dicarboxylic acids having 3 or more and 20 or less carbon atoms.

Linear saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms are not limited to the following, but examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. , sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, diglycolic acid, and the like.
Examples of the branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid and the like.

(Alicyclic dicarboxylic acid unit)
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (hereinafter sometimes referred to as "alicyclic dicarboxylic acid unit") is not limited to the following, for example, an alicyclic structure Alicyclic dicarboxylic acids having 3 or more and 10 or less carbon atoms are included. Among them, as the alicyclic dicarboxylic acid, an alicyclic dicarboxylic acid having an alicyclic structure having 5 or more and 10 or less carbon atoms is preferable.

Examples of such alicyclic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. be done. Among them, 1,4-cyclohexanedicarboxylic acid is preferable as the alicyclic dicarboxylic acid.
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit may be used singly or in combination of two or more.

The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of substituents include alkyl groups having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms are the same as those exemplified in the above "aromatic dicarboxylic acid unit".

The dicarboxylic acid unit other than the isophthalic acid unit preferably contains an aromatic dicarboxylic acid unit, and more preferably contains an aromatic dicarboxylic acid having 6 or more carbon atoms.
By using such a dicarboxylic acid, there is a tendency to obtain a polyamide composition which simultaneously satisfies mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, and the like. In addition, molded articles obtained from polyamide compositions tend to be more excellent in tensile strength, flexural modulus when water is absorbed, and long-term heat resistance.

In the (B) semi-aromatic polyamide, the dicarboxylic acid constituting the (Ba) dicarboxylic acid unit is not limited to the compounds described as the above dicarboxylic acids, and compounds equivalent to the above dicarboxylic acids. good too.
The term "compound equivalent to dicarboxylic acid" as used herein means a compound capable of forming the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, dicarboxylic acid anhydrides and dicarboxylic acid halides.

In addition, (B) the semi-aromatic polyamide may further contain a unit derived from a polycarboxylic acid having a valence of 3 or more, if necessary, as long as the effects of the polyamide composition of the present embodiment are not impaired.
Trivalent or higher polyvalent carboxylic acids include, for example, trimellitic acid, trimesic acid, pyromellitic acid and the like. These trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.

[(Bb) diamine unit]
The (Bb) diamine unit constituting the (B) semi-aromatic polyamide is not particularly limited, and examples thereof include aromatic diamine units, aliphatic diamine units, and alicyclic diamine units. Among them, the (Bb) diamine unit constituting the (B) semi-aromatic polyamide preferably contains a diamine unit having 4 to 10 carbon atoms, and preferably contains a diamine unit having 6 to 10 carbon atoms. more preferred.

(aliphatic diamine unit)
Examples of the aliphatic diamine constituting the aliphatic diamine unit include linear saturated aliphatic diamines having 4 or more and 20 or less carbon atoms.
Examples of straight-chain saturated aliphatic diamines having 4 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine and the like.

(alicyclic diamine unit)
The alicyclic diamine (hereinafter sometimes referred to as "alicyclic diamine") constituting the alicyclic diamine unit is not limited to the following, but examples include 1,4-cyclohexanediamine, 1 ,3-cyclohexanediamine, 1,3-cyclopentanediamine and the like.

(aromatic diamine unit)
The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it contains an aromatic group . Specific examples of aromatic diamines include meta-xylylenediamine and the like.

In addition, the diamine which comprises each diamine unit may be used individually by 1 type, and may be used in combination of 2 or more types.
Among them, the (Bb) diamine unit is preferably an aliphatic diamine unit, more preferably a linear saturated aliphatic diamine unit having 4 to 10 carbon atoms, and a linear saturated aliphatic diamine having 6 to 10 carbon atoms. Group diamine units are more preferred, and hexamethylenediamine units are particularly preferred.
By using such a diamine, there is a tendency to obtain a polyamide composition which simultaneously satisfies mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, and the like. In addition, molded articles obtained from polyamide compositions tend to be more excellent in tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

As the (B) semi-aromatic polyamide contained in the polyamide composition of the present embodiment, polyamide 6I (polyhexamethylene isophthalamide), polyamide 9I, or polyamide 10I is preferable, and polyamide 6I is more preferable. Polyamide 6I is considered to be a suitable material for automotive parts because of its excellent heat resistance, moldability and flame retardancy.

The content of the (B) semi-aromatic polyamide in the polyamide composition of the present embodiment can be 5% by mass or more and 90% by mass or less with respect to the total mass of the polyamide in the polyamide composition, and 10% by mass % or more and 50 mass % or less, more preferably 15.0 mass % or more and 40 mass % or less, and even more preferably 20 mass % or more and 45 mass % or less.
By setting the content of the semi-aromatic polyamide (B) within the above range, the molded article obtained from the polyamide composition has more excellent mechanical properties. In addition, by containing a component typified by (E) a filler, the tensile strength, flexural modulus upon water absorption, and long-term heat resistance of molded articles obtained from the polyamide composition tend to be more excellent.

[(B) Weight average molecular weight Mw (B) of semi-aromatic polyamide]
(B) The weight average molecular weight Mw (B) can be used as an index of the molecular weight of the semi-aromatic polyamide. The weight average molecular weight Mw (B) of the semi-aromatic polyamide is preferably 10000 or more and 50000 or less, more preferably 15000 or more and 45000 or less, still more preferably 15000 or more and 40000 or less, even more preferably 17000 or more and 30000 or less, and 17000 or more and 25000 or less. It is particularly preferred, and 18,000 or more and 22,000 or less is most preferred.
When the weight average molecular weight Mw (B) is in the above range, mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, tensile strength when formed into a molded product, bending elastic modulus when water is absorbed, and long-term A polyamide composition having excellent heat resistance and the like can be obtained.
The weight-average molecular weight Mw(B) can be measured using GPC as described in Examples below.

<Terminal blocking agent>
The ends of the polyamide ((A) aliphatic polyamide and (B) semi-aromatic polyamide) contained in the polyamide composition of the present embodiment may be end-blocked with a known end-blocking agent.
Such a terminal blocking agent is used as a molecular weight modifier when producing a polyamide from the dicarboxylic acid and the diamine, or from at least one selected from the group consisting of the lactam and the aminocarboxylic acid. can be added.

Examples of terminal blocking agents include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides (such as phthalic anhydride), monoisocyanates, monoesters, and monoalcohols. Only one type of terminal blocker may be used alone, or two or more types may be used in combination.
Among them, monocarboxylic acids or monoamines are preferable as terminal blockers. By blocking the ends of the polyamide with a terminal blocking agent, the molded article obtained from the polyamide composition tends to have better thermal stability.

As the monocarboxylic acid that can be used as the terminal blocker, any one having reactivity with the amino group that can be present at the terminal of the polyamide can be used. Examples of monocarboxylic acids include, but are not limited to, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids.
Examples of aliphatic monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. mentioned.
Examples of alicyclic monocarboxylic acids include cyclohexanecarboxylic acid and the like.
Examples of aromatic monocarboxylic acids include benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
These monocarboxylic acids may be used alone or in combination of two or more.
In particular, (B) the terminal of the semi-aromatic polyamide is preferably blocked with acetic acid from the viewpoint of fluidity and mechanical strength.

As the monoamine that can be used as the terminal blocking agent, any one having reactivity with the carboxyl group that may be present at the terminal of the polyamide may be used. Examples of monoamines include, but are not limited to, aliphatic monoamines, alicyclic monoamines, and aromatic monoamines.
Examples of aliphatic monoamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine.
Alicyclic monoamines include, for example, cyclohexylamine and dicyclohexylamine.
Examples of aromatic monoamines include aniline, toluidine, diphenylamine, naphthylamine and the like.
These monoamines may be used individually by 1 type, and may be used in combination of 2 or more types.

Polyamide compositions containing polyamides end-capped with end-capping agents tend to be superior in heat resistance, fluidity, toughness, low water absorption, and rigidity.

<Method for producing (A) aliphatic polyamide and (B) semi-aromatic polyamide>
When producing the polyamide ((A) aliphatic polyamide and (B) semi-aromatic polyamide) contained in the polyamide composition of the present embodiment, the amount of dicarboxylic acid added and the amount of diamine added are about the same molar amount. is preferably Considering the amount of diamine that escapes to the outside of the reaction system during the polymerization reaction, the molar ratio of the total diamine to the total molar amount of dicarboxylic acid is preferably 0.9 or more and 1.2 or less. , is more preferably 0.95 or more and 1.1 or less, and more preferably 0.98 or more and 1.05 or less.

The method for producing polyamide includes, but is not limited to, the following polymerization step (1) or (2).
(1) A step of polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer.
(2) A step of polymerizing at least one selected from the group consisting of lactams constituting lactam units and aminocarboxylic acids constituting aminocarboxylic acid units to obtain a polymer.

Moreover, it is preferable that the method for producing a polyamide further includes an increasing step for increasing the degree of polymerization of the polyamide after the polymerization step. Further, if necessary, a blocking step of blocking terminals of the obtained polymer with a terminal blocking agent may be included after the polymerization step and the rising step.

Specific methods for producing polyamides include, for example, various methods exemplified in 1) to 4) below.
1) Dicarboxylic acid-diamine salts, mixtures of dicarboxylic acids and diamines, lactams, and one or more aqueous solutions or aqueous suspensions selected from the group consisting of aminocarboxylic acids are heated to polymerize while maintaining the molten state. method (hereinafter sometimes referred to as “thermal melt polymerization method”).
2) A method of increasing the degree of polymerization of a polyamide obtained by a hot melt polymerization method while maintaining a solid state at a temperature below the melting point (hereinafter sometimes referred to as "hot melt polymerization/solid phase polymerization method").
3) A method of polymerizing one or more selected from the group consisting of a dicarboxylic acid-diamine salt, a mixture of a dicarboxylic acid and a diamine, a lactam, and an aminocarboxylic acid while maintaining a solid state (hereinafter referred to as "solid phase polymerization (sometimes referred to as “lawful”).
4) A method of polymerizing using a dicarboxylic acid halide component equivalent to the dicarboxylic acid and a diamine component (hereinafter sometimes referred to as "solution method").

Among them, as a specific method for producing a polyamide, a production method including a hot melt polymerization method is preferable. Moreover, when producing a polyamide by a hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to produce the polyamide composition under suitable polymerization conditions. Polymerization conditions include, for example, the conditions shown below. First, the polymerization pressure in the hot melt polymerization method is controlled to 14 kg/cm ² or more and 25 kg/cm ² or less (gauge pressure), and heating is continued. Then, the pressure in the tank is lowered over 30 minutes or more until it reaches the atmospheric pressure (gauge pressure is 0 kg/cm ² ).

In the method for producing polyamide, the form of polymerization is not particularly limited, and may be a batch system or a continuous system.
A polymerization apparatus used for producing polyamide is not particularly limited, and a known apparatus can be used. Specific examples of the polymerization apparatus include an autoclave reactor, a tumbler reactor, and an extruder reactor (kneader, etc.).

As a method for producing a polyamide, a method for producing a polyamide by a batch-type hot-melt polymerization method will be specifically described below, but the method for producing a polyamide is not limited to this.
First, about 40% by mass or more and 60% by mass or less of raw material components for polyamide (combination of dicarboxylic acid and diamine, and at least one selected from the group consisting of lactam and aminocarboxylic acid, if necessary) Prepare an aqueous solution. Then, the aqueous solution is heated to a temperature of 110° C. or higher and 180° C. or lower, and In a concentration tank operated at a pressure of about 0.035 MPa or more and 0.6 MPa or less (gauge pressure), the solution is concentrated to about 65 mass % or more and 90 mass % or less to obtain a concentrated solution.
The resulting concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the autoclave is about 1.2 MPa to 2.2 MPa (gauge pressure).
Then, in an autoclave, the pressure is maintained at about 1.2 MPa or more and 2.2 MPa or less (gauge pressure) while removing at least one of water and gas components. Next, when the temperature reaches approximately 220° C. or higher and 260° C. or lower, the pressure is lowered to atmospheric pressure (gauge pressure is 0 MPa). By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, water produced as a by-product can be effectively removed.
The autoclave is then pressurized with an inert gas such as nitrogen and the polyamide melt is extruded from the autoclave as a strand. The extruded strand is cooled and cut to obtain polyamide pellets.

<Polymer end of polyamide>
The polymer ends of the polyamide ((A) aliphatic polyamide and (B) semi-aromatic polyamide) contained in the polyamide composition of the present embodiment are not particularly limited, but are classified into the following 1) to 4) and defined can do.
2) the carboxy terminus; 3) the capped terminus; 4) the other terminus.
1) The amino terminus is the polymer terminus with an amino group ( _-NH2 group) and is derived from the diamine unit.
2) A carboxy terminus is a polymer terminus having a carboxy group (--COOH group) and is derived from a dicarboxylic acid unit .
3) Terminals formed by a capping agent are terminals formed when a capping agent is added during polymerization. The terminal blocking agent mentioned above is mentioned as a blocking agent.
4) Other terminals are polymer terminals not classified in 1) to 3) above. Specific examples of other terminals include terminals generated by deammonification of amino terminals, terminals generated by decarboxylation of carboxy terminals, and the like.

<(C) Phosphinates>
The (C) phosphinates contained in the polyamide composition of the present embodiment include a phosphinate (phosphinate (1)) represented by the following general formula (1), and a phosphinate (phosphinate (1)) represented by the following general formula (2). diphosphinate (diphosphinate (2)) and at least one phosphinate selected from the group consisting of condensates thereof.

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M ⁿ¹¹⁺ is an n11-valent metal ion M is an element or transition element belonging to Group 2 or Group 15 of the periodic table, n11 is 2 or 3. When n11 is 2 or 3, the plurality of ^R11 and ^R12 are each They may be the same or different.
In general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M′ ^m21+ is an m21 valent metal ion. M' is an element belonging to group 2 or group 15 of the periodic table or a transition element. n21 is an integer of 1 or more and 3 or less. When n21 is 2 or 3, multiple R ²¹ , R ²² and Y ²¹ may be the same or different. m21 is 2 or 3; x is 1 or 2; When x is 2, multiple M' may be the same or different. n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x. )

[R ¹¹ , R ¹² , R ²¹ and R ²² ]
R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. When n11 is 2 or 3, a plurality of R ¹¹ and R ¹² may be the same or different, but are preferably the same for ease of production. When n21 is 2 or 3, the plurality of R ²¹ and R ²² may be the same or different, but are preferably the same for ease of production.
The alkyl group may be chain-like or cyclic, but chain-like is preferred. The chain alkyl group may be linear or branched. Linear alkyl groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like. Examples of branched chain alkyl groups include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 2-methylbutyl group and 3-methylbutyl group. , 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1- Examples include ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group and the like.
Examples of aryl groups include phenyl groups and naphthyl groups.
Alkyl groups and aryl groups may have substituents. Examples of substituents on the alkyl group include aryl groups having 6 or more and 10 or less carbon atoms. Examples of substituents on the aryl group include alkyl groups having 1 to 6 carbon atoms.
Specific examples of the alkyl group having a substituent include a benzyl group and the like.
Specific examples of the aryl group having a substituent include a tolyl group and a xylyl group.
Among them, R ¹¹ , R ¹² , R ²¹ and R ²² are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl or ethyl groups.

[ ^Y21 ]
Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. When n21 is 2 or 3, a plurality of ^Y21 may be the same or different, but are preferably the same for ease of production.
The alkylene group may be chain-like or cyclic, but chain-like is preferred. The chain alkylene group may be linear or branched. Examples of linear alkylene groups include methylene, ethylene, trimethylene, tetramethylene , pentamethylene, and hexamethylene groups. Examples of branched alkylene groups include 1-methylethylene group and 1-methylpropylene group.
The arylene group includes, for example, a phenylene group and a naphthylene group.
An alkylene group and an arylene group may have a substituent. Examples of substituents on the alkylene group include aryl groups having 6 or more and 10 or less carbon atoms. Examples of substituents on the arylene group include alkyl groups having 1 to 6 carbon atoms.
Specific examples of the alkylene group having a substituent include a phenylmethylene group, a phenylethylene group, a phenyltrimethylene group, a phenyltetramethylene group and the like.
Specific examples of the arylene group having a substituent include methylphenylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, tert-butylnaphthylene group and the like.
Among them, Y ²¹ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene group or an ethylene group.

[M and M']
M and M' are each independently an ion of an element belonging to Group 2 or Group 15 of the periodic table , an ion of a transition element , a zinc ion, or an aluminum ion . Examples of ions of elements belonging to Group 2 of the element cycle include calcium ions and magnesium ions. Examples of ions of elements belonging to group 15 of the periodic table include bismuth ions .
Further, when x is 2, the multiple M' may be the same or different, but the same are preferred for ease of production.
Among them, M and M' are preferably calcium, zinc or aluminum, more preferably calcium or aluminum.

[x]
x represents the number of M' and is 1 or 2; x can be appropriately selected according to the type of M' and the number of diphosphinic acids.

[n11 and n21]
n11 represents the number of phosphinic acids and the valence of M, and is 2 or 3; n11 can be appropriately selected according to the type and valence of M.
n21 represents the number of diphosphinic acids and is an integer of 1 or more and 3 or less. n21 can be appropriately selected according to the type and number of M'.

[m21]
m21 represents the valence of M' and is 2 or 3;
n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x.

Specific examples of preferred phosphinates (1) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, and ethylmethylphosphine. aluminum acid, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n - aluminum propylphosphinate, zinc methyl-n-propylphosphinate, calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), benzene-1 , 4-(dimethylphosphinate) calcium, benzene-1,4-(dimethylphosphinate) magnesium, benzene-1,4-(dimethylphosphinate) aluminum, benzene-1,4-(dimethylphosphinate) zinc, methyl Calcium phenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate and the like. Among them, as the phosphinate (1), calcium dimethylphosphinate or aluminum dimethylphosphinate is particularly preferable because of its excellent flame retardancy.

Specific examples of preferred diphosphinates (2) include calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), and benzene-1. ,4-di(methylphosphinate)calcium, benzene-1,4-di(methylphosphinate)magnesium, benzene-1,4-di(methylphosphinate)aluminum, benzene-1,4-di(methylphosphinate) ) zinc and the like.

The method for producing phosphinates is not particularly limited, and examples thereof include the methods described in Patent Documents 5, 6 and 7 and the like. Specifically, it is produced in an aqueous solution using phosphinic acid and a metal carbonate, metal hydroxide or metal oxide. These are essentially monomeric compounds, but also polymeric phosphinates, which are condensates with a degree of condensation of 1 or more and 3 or less, depending on the reaction conditions and under certain circumstances.

(C) The content of phosphinates is 0.1 mass or more with respect to the total mass of (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) phosphinates and (D) polymer % by mass or less is preferable, 5% by mass or more and 30% by mass or less is more preferable, 5% by mass or more and 28% by mass or less is even more preferable, and 8% by mass or more and 25% by mass or less is particularly preferable.
(C) By setting the content of the phosphinic acid salt to the above lower limit or more, it is possible to obtain a polyamide composition that is more excellent in flame retardancy. On the other hand, by setting the content of (C) the phosphinic acid salt to the above upper limit or less, it is possible to obtain a polyamide composition that is more excellent in flame retardancy without impairing the properties of the polyamide copolymer.

<(D) Polymer having an oxygen index of 27% or more and having an aromatic group in the main chain>
The (D) polymer contained in the polyamide composition of the present embodiment is not particularly limited as long as it has an oxygen index of 27% or more. Specific examples of (D) polymers include polyphenylene sulfide, polyphenylene ether, maleic anhydride-modified polyphenylene ether, polysulfone, polyetheretherketone, polyetherimide, polyamideimide, and polyethersulfone. Among them, the (D) polymer is preferably polyphenylene sulfide, polyphenylene ether, maleic anhydride-modified polyphenylene ether or polysulfone, and particularly preferably polyphenylene sulfide, polyphenylene ether or maleic anhydride-modified polyphenylene ether.

In general, the "oxygen index" is an index of the flammability of a material, and is expressed by the minimum oxygen concentration (% by volume) required for the material to sustain combustion. Oxygen index can be measured according to ISO 4589-2.

(D) The content of the polymer is 0.1% by mass or more with respect to the total mass of (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) phosphinic acid salts and (D) polymer 8.0 % by mass or less, preferably 1.0% by mass or more and 8.0% by mass or less, more preferably 2.5% by mass or more and 8.0% by mass or less, and 2.5% by mass or more and 6.5% by mass or less More preferred.
By setting the content of the polymer (D) to the above lower limit or more, it is possible to obtain a polyamide composition that is more excellent in flame retardancy. On the other hand, by setting the content of the polymer (D) to the above upper limit or less, it is possible to obtain a polyamide composition that is more excellent in long-term heat resistance.
Further, by setting the content of the polymer (D) within the above range, it is possible to obtain a polyamide composition which is excellent in flexural modulus upon water absorption and long-term heat resistance.

[(D) polymer weight average molecular weight Mw (D)]
(D) As an index of the molecular weight of the polymer, the weight average molecular weight Mw (D) can be used. (D) The weight average molecular weight Mw (D) of the polymer is preferably 10000 or more and 70000 or less, more preferably 15000 or more and 60000 or less, still more preferably 20000 or more and 60000 or less, even more preferably 25000 or more and 60000 or less, and 25000 or more and 55000 or less. It is particularly preferred, and 30,000 or more and 55,000 or less is most preferred.
When the weight average molecular weight Mw (D) is in the above range, mechanical properties, particularly water absorption stiffness, heat stiffness, fluidity, tensile strength when formed into a molded product, bending elastic modulus when water is absorbed, and long-term A polyamide composition having excellent heat resistance and the like can be obtained.
The weight average molecular weight Mw(D) can be measured using GPC as described in the examples below.

<(E) Filler>
The polyamide composition of the present embodiment may further contain (E) a filler in addition to the above components (A) to (D). By containing (E) a filler, it is possible to obtain a polyamide composition having better mechanical properties such as toughness and rigidity.

The (E) filler contained in the polyamide composition of the present embodiment is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, and glass. Flakes, talc, kaolin, mica, hydrotalcite, zinc carbonate, calcium monohydrogen phosphate, wollastonite, zeolite, boehmite, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black , furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling fluoromica, apatite and the like.
These (E) fillers may be used singly or in combination of two or more.
Among them, from the viewpoint of rigidity and strength, the (E) filler includes glass fiber, carbon fiber, glass flake, talc, kaolin, mica, calcium monohydrogen phosphate, wollastonite, carbon nanotube, graphite, fluoride Calcium, montmorillonite, swelling fluoromica or apatite are preferred. As the (E) filler, glass fiber or carbon fiber is more preferred, and glass fiber is even more preferred.

(E) When the filler is glass fiber or carbon fiber, the number average fiber diameter (D) is preferably 3 μm or more and 30 μm or less. Also, the weight average fiber length (L) is preferably 100 μm or more and 750 μm or less. Further, the aspect ratio ((L)/(D)) of the number average fiber diameter (D) to the weight average fiber length (L) is preferably 10 or more and 100 or less. By using the glass fiber or carbon fiber having the above structure, higher properties can be exhibited.
Moreover, when (E) the filler is glass fiber, it is more preferable that the number average fiber diameter (D) is 3 μm or more and 30 μm or less. More preferably, the weight average fiber length (L) is 103 μm or more and 500 μm or less. Furthermore, the aspect ratio ((L)/(D)) of 3 or more and 100 or less is more preferable.

(E) The number average fiber diameter and weight average fiber length of the filler can be measured using the following methods.
First, a molded article of a polyamide composition is dissolved in a solvent such as formic acid in which polyamide is soluble. Then, for example, 100 or more fillers are arbitrarily selected from the obtained insoluble components. Then, it can be obtained by observing the filler with an optical microscope, a scanning electron microscope, or the like.

The content of the (E) filler in the polyamide composition is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, relative to the total mass of the polyamide composition, and 15% by mass % or more and 60 mass % or less is more preferable, 20 mass % or more and 50 mass % or less is particularly preferable, and 25 mass % or more and 40 mass % or less is most preferable.
(E) When the content of the filler is at least the above lower limit, mechanical properties such as strength and rigidity of the polyamide composition tend to be further improved. On the other hand, when the content of the filler (E) is equal to or less than the above upper limit, it tends to be possible to obtain a polyamide composition having more excellent moldability.
In particular, (E) the filler is glass fiber, and the content of (E) the filler is within the above range with respect to the total mass of the polyamide composition, so that the strength, rigidity, etc. of the polyamide composition mechanical properties tend to be further improved.

<(F) Other additives>
In the polyamide composition of the present embodiment, in addition to the above components (A) to (E), (F) commonly used in polyamides within a range that does not impair the effects of the polyamide composition of the present embodiment Other additives can also be contained. Examples of (F) other additives include (F1) moldability improver, (F2) deterioration inhibitor, (F3) nucleating agent, (F4) heat stabilizer and the like.
The content of (F) other additives in the polyamide composition of the present embodiment varies depending on the type and application of the polyamide composition, so long as it does not impair the effects of the polyamide composition of the present embodiment. There are no particular restrictions.

[(F1) moldability improver]
The moldability improver (F1) contained in the polyamide composition of the present embodiment is not particularly limited, but examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like. The formability improver is also used as a "lubricant".

(higher fatty acid)
Examples of higher fatty acids include linear or branched, saturated or unsaturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms.
Examples of linear saturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid and montanic acid.
Examples of branched-chain saturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include isopalmitic acid and isostearic acid.
Examples of linear unsaturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include oleic acid and erucic acid.
Examples of branched unsaturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms include isoleic acid.
Among them, stearic acid or montanic acid is preferable as the higher fatty acid.

(Higher fatty acid metal salt)
A higher fatty acid metal salt is a metal salt of a higher fatty acid.
Examples of the metal elements of the metal salt include Group 1 elements, Group 2 elements and Group 3 elements of the periodic table, zinc, and aluminum.
Examples of Group 1 elements of the periodic table include sodium and potassium.
Group 2 elements of the periodic table of elements include, for example, calcium and magnesium.
Group 3 elements of the periodic table of elements include, for example, scandium and yttrium.
Among them, elements of groups 1 and 2 of the periodic table or aluminum are preferable, and sodium, potassium, calcium, magnesium or aluminum is more preferable.

Specific examples of higher fatty acid metal salts include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, and calcium palmitate.
Among them, as the higher fatty acid metal salt, a metal salt of montanic acid or a metal salt of stearic acid is preferable.

(higher fatty acid ester)
Higher fatty acid esters are esters of higher fatty acids and alcohols.
As the higher fatty acid ester, an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.
Examples of aliphatic alcohols having 8 to 40 carbon atoms include stearyl alcohol, behenyl alcohol, and lauryl alcohol.
Specific examples of higher fatty acid esters include stearyl stearate and behenyl behenate.

(higher fatty acid amide)
A higher fatty acid amide is an amide compound of a higher fatty acid.
Examples of higher fatty acid amides include stearic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearylamide, ethylenebisoleylamide, N-stearyl stearic acid amide, N-stearyl erucic acid amide and the like.
These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides may be used singly or in combination of two or more.

[(F2) deterioration inhibitor]
The (F2) deterioration inhibitor contained in the polyamide composition of the present embodiment is used for the purpose of preventing thermal deterioration and discoloration when heated, and improving heat aging resistance.
(F2) The deterioration inhibitor is not particularly limited, but examples include copper compounds, phenolic stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, benzotriazole stabilizers, and benzophenone stabilizers. , cyanoacrylate stabilizers, salicylate stabilizers, sulfur stabilizers, and the like.
Examples of copper compounds include copper acetate and copper iodide.
Phenolic stabilizers include, for example, hindered phenol compounds.
These (F2) deterioration inhibitors may be used singly or in combination of two or more.

[(F3) Nucleating agent]
(F3) The nucleating agent means a substance that can obtain at least one of the following effects (1) to (3) when added.
(1) Effect of raising the crystallization peak temperature of the polyamide composition.
(2) The effect of reducing the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak.
(3) Effect of refining the spherulites of the resulting molded product or uniformizing the size thereof.

(F3) Nucleating agents include, but are not limited to, talc, boron nitride, mica, kaolin, silicon nitride, carbon black, potassium titanate, molybdenum disulfide, and the like.
(F3) The nucleating agent may be used alone or in combination of two or more.
Among them, talc or boron nitride is preferable as the (F3) nucleating agent from the viewpoint of the effect of the nucleating agent.

Further, since the effect of the nucleating agent is high, the number average particle diameter of the nucleating agent (F3) is preferably 0.01 μm or more and 10 μm or less.
The number average particle size of the nucleating agent can be measured using the following method. First, the molded article is dissolved in a solvent such as formic acid in which polyamide is soluble. Then, for example, 100 or more nucleating agents are arbitrarily selected from the obtained insoluble components. Then, it can be obtained by observing with an optical microscope, a scanning electron microscope, or the like and measuring the particle size.

The content of the nucleating agent in the polyamide composition of the present embodiment is 0.001 parts by mass or more and 1 part by mass with respect to 100 parts by mass of polyamide ((A) aliphatic polyamide and (B) semi-aromatic polyamide) The following is preferable, 0.001 to 0.5 parts by mass is more preferable, and 0.001 to 0.09 parts by mass is even more preferable.
By setting the content of the nucleating agent to 100 parts by mass of the polyamide or more, the heat resistance of the polyamide composition tends to be further improved. A polyamide composition having excellent toughness can be obtained by adjusting the content to be equal to or less than the above upper limit with respect to 100 parts by mass.

[(F4) Thermal stabilizer]
(F4) The heat stabilizer is not limited to the following, but includes, for example, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, groups 3 and 4 of the periodic table, and groups 11 to Metal salts of Group 14 elements and the like are included.

(Phenolic heat stabilizer)
Phenolic heat stabilizers include, but are not limited to, hindered phenol compounds. Hindered phenol compounds have the property of imparting excellent heat resistance and light resistance to resins such as polyamides and fibers.
Examples of the hindered phenol compound include, but are not limited to, N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylprop onamide), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propynyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,5-di-t -butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5 -tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and the like.
These hindered phenol compounds may be used singly or in combination of two or more.

When using a phenolic heat stabilizer, the content of the phenolic heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less with respect to the total mass of the polyamide composition, and 0.05 % by mass or more and 1 mass % or less is more preferable.
When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be further reduced.

(Phosphorus heat stabilizer)
Examples of phosphorus-based heat stabilizers include, but are not limited to, pentaerythritol-type phosphite compounds, trioctylphosphite, trilaurylphosphite, tridecylphosphite, octyldiphenylphosphite, trisisodecyl Phosphite, phenyldiisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl(tridecyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2 ,4-di-t-butylphenyl)phosphite, tris(2,4-di-t-butyl-5-methylphenyl)phosphite, tris(butoxyethyl)phosphite, 4,4'-butylidene-bis( 3-methyl-6-t-butylphenyl-tetra-tridecyl)diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidenebis(2-t -butylphenyl)-di(nonylphenyl)phosphite, tris(biphenyl)phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butanedi Phosphites, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenyl) diphosphite, tetra(C1-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tris (mono, dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebis(2-t-butylphenyl)-di(nonylphenyl)phosphite, 9,10-di-hydro-9-oxa - 10- Phosphaphenanthrene-10-oxide, tris(3,5-di-t-butyl-4-hydroxyphenyl)phosphite, hydrogenated-4,4'-isopropylidene diphenyl polyphosphite, bis(octylphenyl) -bis(4,4'-butylidenebis(3-methyl-6-t-butylphenyl))-1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris(2-methyl-4- hydroxy-5-t-butylphenyl)diphosphite, tris(4,4'-isopropylidenebis(2-t-butylphenyl))phosphite, tris(1,3-stearoyloxyisopropyl)phosphite, 2,2- methylenebis(4,6-di-t-butylphenyl)octylphosphite, 2,2-methylenebis(3-methyl-4,6-di-t-butylphenyl)2-ethylhexylphosphite, tetrakis(2,4- di-t-butyl-5-methylphenyl)-4,4'-biphenylenediphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenediphosphite and the like.
These phosphorus-based heat stabilizers may be used alone or in combination of two or more.

Examples of pentaerythritol-type phosphite compounds include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl -pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve-pentaerythritol Diphosphite, 2,6-di-t-butyl-4-methylphenyl-butylcarbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite phosphites, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, Bis(2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,6-di-t-butylphenyl-penta Erythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-2,4-di-t-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di -t-amyl-4-methylphenyl-phenyl pentaerythritol diphosphite, bis(2,6-di-t-amyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di -t-octyl-4-methylphenyl)pentaerythritol diphosphite and the like.
These pentaerythritol-type phosphite compounds may be used alone or in combination of two or more.

When using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less with respect to the total mass of the polyamide composition, and 0.05 % by mass or more and 1 mass % or less is more preferable.
When the content of the phosphorus-based heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.

(Amine heat stabilizer)
Examples of amine heat stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6, 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2 ,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl)-carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl)-oxalate, bis(2,2,6,6-tetra methyl-4-piperidyl)-malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)-adipate, bis (2,2,6,6-tetramethyl-4-piperidyl)-terephthalate, 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-ethane, α,α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl tolylene-2,4-dicarbamate, bis ( 2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3, 5-tricarboxylate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di -t-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethyl Piperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-[2 ,4,8,10-tetraoxaspiro(5,5)undecane]condensates with diethanol.
These amine heat stabilizers may be used alone or in combination of two or more.

When using an amine-based heat stabilizer, the content of the amine-based heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less with respect to the total mass of the polyamide composition, and 0.05 % by mass or more and 1 mass % or less is more preferable.
When the content of the amine-based heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.

(Metal salts of elements of groups 3, 4 and 11 to 14 of the periodic table)
The metal salts of elements belonging to Groups 3, 4 and 11 to 14 of the periodic table are not particularly limited as long as they are salts of metals belonging to these groups.
Among them, copper salts are preferable from the viewpoint of further improving the heat aging resistance of the polyamide composition. Examples of such copper salts include, but are not limited to, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, chelating agents includes copper complex salts in which copper is coordinated.
Chelating agents include, for example, ethylenediamine and ethylenediaminetetraacetic acid.
These copper salts may be used singly or in combination of two or more.
Among them, copper acetate is preferable as the copper salt. When copper acetate is used, a polyamide composition that is superior in heat aging resistance and can more effectively suppress metal corrosion (hereinafter sometimes simply referred to as "metal corrosion") of screw and cylinder parts during extrusion is provided. can get.

(F4) When using a copper salt as a heat stabilizer, the content of the copper salt in the polyamide composition is 0 with respect to the total mass of the polyamide ((A) aliphatic polyamide and (B) semi-aromatic polyamide) 0.01% by mass or more and 0.60% by mass or less is preferable, and 0.02% by mass or more and 0.40% by mass or less is more preferable.
When the content of the copper salt is within the above range, the heat aging resistance of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be more effectively suppressed.

Further, the content concentration of the copper element derived from the above copper salt is, from the viewpoint of improving the heat aging resistance of the polyamide composition, polyamide ((A) aliphatic polyamide and (B) semi-aromatic polyamide) 10 ⁶ parts by mass (1,000,000 parts by mass), preferably 10 parts by mass or more and 2000 parts by mass or less, more preferably 30 parts by mass or more and 1500 parts by mass or less, and even more preferably 50 parts by mass or more and 500 parts by mass or less.

The component (F4) heat stabilizer explained above may be used alone or in combination of two or more.

<<Method for producing polyamide composition>>
As a method for producing the polyamide composition of the present embodiment, (A) an aliphatic polyamide, the components (B) to (D) above, and, if necessary, the components (E) and (F) and is not particularly limited as long as it is a method of mixing.

As a method for mixing each component of (A) to (D) above and, if necessary, each component of (E) and (F), for example, the following method (1) or (2) etc.
(1) Components (A) to (D) above and, if necessary, components (E) and (F) are mixed using a Henschel mixer or the like, fed to a melt kneader and kneaded. Method.
(2) In a single-screw or twin-screw extruder, each of the above components (A) to (D) and, if necessary, the component (E) are mixed in advance using a Henschel mixer or the like (A) After preparing a mixture containing each component of ~ (D) and, if necessary, the (F) component, supplying the mixture to a melt kneader and kneading, optionally, the (E) component is added from the side feeder how to compound.

As for the method of supplying the components constituting the polyamide composition to the melt kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports.

The melt-kneading temperature is preferably a temperature higher than the melting point of the (A) aliphatic polyamide by about 1° C. or higher and 100° C. or lower, more preferably a temperature higher than the melting point of the (A) aliphatic polyamide by about 10° C. or higher and 50° C. or lower.
The shear rate in the kneader is preferably about 100 sec ^-1 or more. Also, the average residence time during kneading is preferably about 0.5 minutes or more and 5 minutes or less.
As a device for melt-kneading, any known device may be used, and for example, a single-screw or twin-screw extruder, a Banbury mixer, a melt-kneader (mixing roll, etc.), etc. are preferably used.
The blending amount of each component when producing the polyamide composition of the present embodiment is the same as the content of each component in the polyamide composition described above.

≪Molded product≫
The molded article of this embodiment is obtained by molding the polyamide composition of the above embodiment.
The molded article of the present embodiment does not contain halogen, is excellent in flame retardancy, and has excellent tensile strength, flexural modulus upon water absorption, and long-term heat resistance.

A method for obtaining a molded article is not particularly limited, and a known molding method can be used.
Examples of known molding methods include extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, molding of other materials, gas assist injection molding, foam injection molding, low pressure molding, and ultra-thin injection molding. (ultra-high-speed injection molding), in-mold compound molding (insert molding, outsert molding), and the like.

<Application>
The molded article of this embodiment contains the polyamide composition of the above embodiment, is excellent in flame retardancy and mechanical properties (especially, flexural modulus when absorbing water, long-term heat resistance, etc.), and can be used for various purposes. can be done.
Applications of the molded product of the present embodiment include, for example, the automotive field, the electrical and electronic field, the mechanical and industrial field, the office equipment field, and the aviation and space field.

EXAMPLES The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

Each component of the polyamide compositions used in Examples and Comparative Examples will be described below.

<Constituent>
[(A) Aliphatic Polyamide]
A-1: Polyamide 66
A-2: Polyamide 6 (manufactured by Ube Industries, model number: SF1013A, molecular weight: 33000)

[(B) Semi-aromatic polyamide]
B-1: Polyamide 6I
B-2: Polyamide 6I/6T (manufactured by Ems, model number: G21, isophthalic acid unit content in all dicarboxylic acid units: 70 mol%, molecular weight: 27000)
B-3: Polyamide MXD6 (manufactured by Toyobo Co., Ltd., trade name: Toyobo Nylon, T-600)

[(C) Phosphinates]
C-1: Phosphinic acid-based flame retardant aluminum diethylphosphinate (manufactured by Clariant, trade name: "Exolit OP1230")
C-2: Phosphinic acid-based flame retardant calcium diethylphosphinate (manufactured by Taihei Kagaku Sangyo Co., Ltd.)

[(C') Flame retardant other than phosphinate]
C'-1: Nitrogen-based flame retardant melamine cyanurate (manufactured by Nissan Chemical Industries, Ltd.)
C'-2: Nitrogen and phosphorus-based flame retardant Cyclic phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd.)

[(D) Polymer having an oxygen index of 27% or more and having an aromatic group in the main chain]
D-1: Polyphenylene sulfide (PPS) (manufactured by DIC) (oxygen index: 46%, molecular weight: 30000)
D-2: Maleic anhydride-modified polyphenylene ether (m-PPE) (manufactured by Asahi Kasei Corporation) (oxygen index: 28%, molecular weight: 54000)
D-3: Polyphenylene ether (PPE) (manufactured by Asahi Kasei Corporation) (oxygen index: 28%, molecular weight: 30000)
D-4: Polysulfone (PSF) (manufactured by Solvay) (oxygen index: 30%, molecular weight: 50000)

[(D') Polymer having an oxygen index of less than 27% or having no aromatic group in the main chain]
D'-1: Polycarbonate (PC) (manufactured by Teijin Ltd.) (oxygen index: 25%, molecular weight: 40000)
D'-2: Polyvinyl chloride (PVC) (manufactured by Taiyo PVC Co., Ltd.) (oxygen index: 30%, molecular weight: 97000)
The oxygen indices of the (D) polymer and the (D') polymer were measured according to ISO 4589-2.

[(E) filler]
E-1: Glass fiber (GF) (manufactured by Nippon Electric Glass, trade name “ECS03T275H” average fiber diameter 10 μmφ, cut length 3 mm)

[(F) Other additives]
F-1: Phenolic heat stabilizer (manufactured by Ciba Specialty Chemicals, trade name: "Irganox 1098")

<Production of Polyamide>
Each method for producing the aliphatic polyamide A-1 and the semi-aromatic polyamide B-1 will be described in detail below. The aliphatic polyamide A-1 and the semi-aromatic polyamide B-1 obtained by the following production method were dried in a nitrogen stream to adjust the moisture content to about 0.2% by mass, and then It was used as a raw material for polyamide compositions in Examples and Comparative Examples described later.

[Synthesis Example 1] Synthesis of Aliphatic Polyamide A-1 (Polyamide 66) Polymerization reaction of polyamide was carried out as follows by the “hot melt polymerization method”.
First, 1500 g of an equimolar salt of adipic acid and hexamethylenediamine was dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass uniform aqueous solution of the raw material monomer. This aqueous solution was charged into an autoclave having an internal volume of 5.4 L, and was purged with nitrogen. Then, while stirring at a temperature of about 110° C. or higher and 150° C. or lower, the solution was concentrated by removing steam gradually until the solution concentration reached 70% by mass. The internal temperature was then raised to 220°C. At this time, the autoclave was pressurized to 1.8 MPa. The mixture was allowed to react for 1 hour while the pressure was maintained at 1.8 MPa by gradually removing water vapor until the internal temperature reached 245°C. The pressure was then reduced over 1 hour. Then, the inside of the autoclave was maintained under a reduced pressure of 650 torr (86.66 kPa) for 10 minutes using a vacuum device. At this time, the final internal temperature of the polymerization was 265°C. Then, it was pressurized with nitrogen, made into a strand from a lower spinneret (nozzle), water-cooled and cut, and discharged in the form of pellets. The pellets were then dried at 100° C. under a nitrogen atmosphere for 12 hours to obtain aliphatic polyamide A-1 (polyamide 66).
The resulting aliphatic polyamide A-1 (polyamide 66) had Mw (A)=40,000.

[Synthesis Example 2] Synthesis of Semi-Aromatic Polyamide B-1 (Polyamide 6I) Polymerization reaction of polyamide was carried out as follows by the “hot melt polymerization method”.
First, equimolar salt of isophthalic acid and hexamethylenediamine: 1500 g, and 1.5 mol % excess adipic acid and 0.5 mol % acetic acid with respect to all equimolar salt components, distilled water: 1500 g to prepare an equimolar 50% by mass uniform aqueous solution of the raw material monomer. Then, while stirring at a temperature of about 110° C. or higher and 150° C. or lower, the solution was concentrated by removing steam gradually until the solution concentration reached 70% by mass. The internal temperature was then raised to 220°C. At this time, the autoclave was pressurized to 1.8 MPa. The mixture was allowed to react for 1 hour while the pressure was maintained at 1.8 MPa by gradually removing water vapor until the internal temperature reached 245°C. The pressure was then reduced over 30 minutes. Then, the inside of the autoclave was maintained under a reduced pressure of 650 torr (86.66 kPa) for 10 minutes using a vacuum device. At this time, the final internal temperature of the polymerization was 265°C. Then, it was pressurized with nitrogen, made into a strand from a lower spinneret (nozzle), water-cooled and cut, and discharged in the form of pellets. The pellets were then dried at 100° C. under a nitrogen atmosphere for 12 hours to obtain a semi-aromatic polyamide B-1 (polyamide 6I).
The resulting semi-aromatic polyamide B-1 (polyamide 6I) had a content of isophthalic acid units in dicarboxylic acid units of 100 mol %. Mw=20,000.

<Physical properties and evaluation>
First, the polyamide composition pellets obtained in Examples and Comparative Examples were dried in a nitrogen stream to reduce the water content in the polyamide composition to 500 ppm or less. Next, using the pellets of each polyamide composition with adjusted moisture content, various physical properties were measured and various evaluations were performed using the following methods.

[Physical properties 1] tan δ peak temperature Using a PS40E injection molding machine manufactured by Nissei Kogyo Co., Ltd., setting the cylinder temperature to 290 ° C. and the mold temperature to 100 ° C., injection molding conditions of 10 seconds for injection and 10 seconds for cooling, JIS- A molded product was molded according to K7139. This molded article was measured under the following conditions using a dynamic viscoelasticity evaluation device (manufactured by GABO, EPLEXOR500N).

(Measurement condition)
Measurement mode: Tensile Measurement frequency: 8.00Hz
Heating rate: 3°C/min Temperature range: -100 to 250°C

The ratio (E2/E1) of the storage elastic modulus E1 and the loss elastic modulus E2 was defined as tan δ, and the highest temperature was defined as the tan δ peak temperature.

[Physical property 2] Molecular weight (Mw) of polyamide composition
The weight average molecular weights (Mw) of the polyamide compositions obtained in Examples and Comparative Examples were measured using GPC under the following measurement conditions.

(Measurement condition)
Measuring device: HLC-8020 manufactured by Tosoh Corporation
Solvent: Hexafluoroisopropanol Solvent standard sample: PMMA (polymethyl methacrylate) (manufactured by Polymer Laboratories) conversion GPC column: TSK-GEL GMHHR-M and G1000HHR

[Evaluation 1] Flame Retardancy Measured using the method of UL94 (the standard established by Under Writers Laboratories Inc., USA). The test piece (length 127 mm, width 12.7 mm, thickness 1.6 mm) was prepared by attaching a mold for the UL test piece (mold temperature = 100°C) to an injection molding machine (PS40E manufactured by Nissei Kogyo Co., Ltd.). and the cylinder temperature: 290°C, and by molding each polyamide composition. The injection pressure was the full filling pressure + 2% pressure when molding the UL test piece. The flame retardant grade was evaluated according to the UL94 standard (vertical burning test) to determine which grade was V-0, V-1, or V-2. In addition, the flame retardance is so high that the numerical value of a grade is small.

[Evaluation 2] Tensile strength Using an injection molding machine [PS-40E: manufactured by Nissei Plastics Co., Ltd.], each polyamide composition was molded into a multi-purpose test piece A type molded piece according to ISO 3167. Specific molding conditions were as follows: injection + holding pressure time: 25 seconds, cooling time: 15 seconds, mold temperature: 80°C, molten resin temperature: melting peak temperature (Tm2) on the high temperature side of polyamide + 20°C.
Using the obtained multi-purpose test piece A molded piece, a tensile test was performed at a tensile speed of 5 mm / min under a temperature condition of 23 ° C. in accordance with ISO 527, and the tensile yield stress was measured and used as the tensile strength. .

[Evaluation 3] Flexural modulus at the time of water absorption An ISO dumbbell having a thickness of 4 mm was produced and used as a test piece. Using the obtained test piece, the flexural modulus was measured according to ISO 178. In addition, the ISO dumbbell was left in an atmosphere of constant temperature and humidity (23° C., 50 RH %) to reach water absorption equilibrium, and then the flexural modulus was measured according to ISO 178.

[Evaluation 4] Long-Term Heat Resistance A multi-purpose test piece (Type A) for the above tensile strength was heated at 150° C. in a hot air circulating oven for heat aging.
After 1000 hours from placing in the oven, it was removed from the oven and cooled at 23° C. for 24 hours or more. Next, the multi-purpose test piece (type A) after cooling was subjected to a tensile test in accordance with ISO 527 at a tensile speed of 5 mm/min by the same method as described above to measure each tensile strength. The heat aging retention rate was obtained using the following formula.

Heat-resistant aging retention rate (%) = Tensile strength after aging/Tensile strength before aging x 100

[Evaluation 5] Tracking Resistance A test piece having a size of 30 mm×30 mm and a thickness of 4 mm was prepared, and the CTI was measured according to the IEC60112 standard. In addition, the applied voltage was performed in units of 50V.
According to the obtained comparative tracking index (TI), they were ranked as follows.

(Ranking)
CTI Class 0: 600≤TI
CTI Grade 1: 400≤TI<600
CTI Grade 2: 250≤TI<400
CTI Grade 3: 175≤TI<250
CTI Grade 4: 100≤TI<175
CTI Class 5: 0≤TI<100

[Example 1] Production of polyamide composition P-1a Using a TEM 35 mm twin-screw extruder (set temperature: 280 ° C., screw rotation speed 300 rpm) manufactured by Toshiba Machine Co., Ltd., a top feed port provided at the most upstream part of the extruder From, (A) aliphatic polyamide A-1, (B) semi-aromatic polyamide B-1, (D) polymer D-1, and (F) other additive F-1 pre-blended, supplied. In addition, (C) flame retardant C-1 and (E) filler E-1 were supplied from the side feed port on the downstream side of the extruder (the state in which the resin supplied from the top feed port is sufficiently melted). . Next, the melt-kneaded product extruded from the die head was cooled in a strand form and pelletized to obtain pellets of the polyamide composition P-1a. The blending amount is (A) aliphatic polyamide A-1: 46.0% by mass, (B) semi-aromatic polyamide B-1: 11.6% by mass, (C) flame retardant C-1: 16.0% by mass , (D) polymer D-1: 1.0% by mass, (E) filler E-1: 25.0% by mass, and (F) other additive F-1: 0.1% by mass.

[Example 2] Production of polyamide composition P-2a The blending amount was (A) aliphatic polyamide A-1: 45.2% by mass, (B) semi-aromatic polyamide B-1: 11.4% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-2a were obtained in the same manner as in Example 1, except that the content was changed to 2.0% by mass.

[Example 3] Production of polyamide composition P-3a The blending amount was (A) aliphatic polyamide A-1: 44.4% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-3a were obtained in the same manner as in Example 1, except that the polymer was changed to 3.0% by mass.

[Example 4] Production of polyamide composition P-4a The blending amount was (A) aliphatic polyamide A-1: 43.6% by mass, (B) semi-aromatic polyamide B-1: 11.0% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-4a were obtained in the same manner as in Example 1, except that the polymer was changed to 4.0% by mass.

[Example 5] Production of polyamide composition P-5a The blending amounts were (A) aliphatic polyamide A-1: 46.2% by mass, (B) semi-aromatic polyamide B-1: 11.6% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-5a were obtained in the same manner as in Example 1, except that the content was changed to 1.0% by mass.

[Example 6] Production of polyamide composition P-6a The blending amount was (A) aliphatic polyamide A-1: 44.6% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-6a were obtained in the same manner as in Example 1, except that the polymer was changed to 3.0% by mass.

[Example 7] Production of polyamide composition P-7a The blending amount was (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-7a were obtained in the same manner as in Example 1, except that the content was changed to 5.0% by mass.

[Example 8] Production of polyamide composition P-8a The blending amount was (A) aliphatic polyamide A-1: 40.0% by mass, (B) semi-aromatic polyamide B-1: 10.0% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-8a were obtained in the same manner as in Example 1, except that the content was changed to 5.7% by mass.

[Example 9] Production of polyamide composition P-9a The blending amount was (A) aliphatic polyamide A-1: 44.4% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) Polymer D-3: Pellets of polyamide composition P-9a were obtained in the same manner as in Example 1, except that the polymer was changed to 3.0% by mass.

[Example 10] Production of polyamide composition P-10a The blending amount was (A) aliphatic polyamide A-1: 44.4% by mass, (B) semi-aromatic polyamide B-1: 11.2% by mass, and (D) Polymer D-4: Pellets of polyamide composition P-10a were obtained in the same manner as in Example 1, except that the polymer was changed to 3.0% by mass.

[Example 11] Production of polyamide composition P-11a The blending amount was (A) aliphatic polyamide A-1: 45.2% by mass, (B) semi-aromatic polyamide B-2: 11.4% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-11a were obtained in the same manner as in Example 1, except that the content was changed to 2.0% by mass.

[Example 12] Production of polyamide composition P-12a The blending amount was (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-2: 10.8% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-12a were obtained in the same manner as in Example 1, except that the polymer was changed to 5.0% by mass.

[Example 13] Production of polyamide composition P-13a The blending amount was (A) aliphatic polyamide A-2: 45.2% by mass, (B) semi-aromatic polyamide B-1: 11.4% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-13a were obtained in the same manner as in Example 1, except that the content was changed to 2.0% by mass.

[Example 14] Production of polyamide composition P-14a The blending amount was (A) aliphatic polyamide A-2: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-14a were obtained in the same manner as in Example 1, except that the polymer was changed to 5.0% by mass.

[Example 15] Production of polyamide composition P-15a The blending amount was (A) aliphatic polyamide A-1: 48.2% by mass, (B) semi-aromatic polyamide B-1: 5.4% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-15a were obtained in the same manner as in Example 1, except that the polymer was changed to 5.0% by mass.

[Example 16] Production of polyamide composition P-16a The blending amount was (A) aliphatic polyamide A-1: 37.5% by mass, (B) semi-aromatic polyamide B-1: 16.1% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-16a were obtained in the same manner as in Example 1, except that the polymer was changed to 5.0% by mass.

[Example 17] Production of polyamide composition P-17a The blending amount was (A) aliphatic polyamide A-1: 32.2% by mass, (B) semi-aromatic polyamide B-1: 21.4% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-17a were obtained in the same manner as in Example 1, except that the content was changed to 5.0% by mass.

[Example 18] Production of polyamide composition P-18a The blending amount is (A) aliphatic polyamide A-1: 29.4% by mass, (B) semi-aromatic polyamide B-1: 7.4% by mass, ( C) Phosphinate C-1: 9.0% by mass, (D) Polymer D-2: 3.8% by mass, and (E) Filler: Same as in Example 1 except that it was changed to 50% by mass method was used to obtain pellets of polyamide composition P-18a.

[Example 19] Production of polyamide composition P-19a The blending amount is (A) aliphatic polyamide A-1: 22.2% by mass, (B) semi-aromatic polyamide B-1: 14.6% by mass, ( C) Phosphinate C-1: 9.0% by mass, (D) Polymer D-2: 3.8% by mass, and (E) Filler: Same as Example 1 except that it was changed to 50.0% by mass. A similar method was used to obtain pellets of polyamide composition P-19a.

[Example 20] Production of polyamide composition P-20a The blending amount is (A) aliphatic polyamide A-1: 39.6% by mass, (B) semi-aromatic polyamide B-1: 10.0% by mass, ( C) Phosphinate C-2: 20.0% by mass, (D) Polymer D-2: 5.0% by mass using the same method as in Example 1, polyamide composition P-20a of pellets were obtained.

[Example 21] Production of polyamide composition P-21a The blending amount is (A) aliphatic polyamide A-1: 7.0% by mass, (B) semi-aromatic polyamide B-3: 46.6% by mass, ( C) Phosphinates C-1: 16.0% by mass, (D) Polymer D-2: 5.0% by mass using the same method as in Example 1, polyamide composition P-21a of pellets were obtained.

[Comparative Example 1] Production of polyamide composition P-1b The blending amount was (A) aliphatic polyamide A-1: 46.8% by mass, (B) semi-aromatic polyamide B-1: 11.8% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-1b were obtained in the same manner as in Example 1, except that the polymer was changed to 0% by mass.

[Comparative Example 2] Production of polyamide composition P-2b The blending amount was (A) aliphatic polyamide A-1: 46.8% by mass, (B) semi-aromatic polyamide B-2: 11.8% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-2b were obtained in the same manner as in Example 1, except that the polymer was changed to 0% by mass.

[Comparative Example 3] Production of polyamide composition P-3b The blending amount was (A) aliphatic polyamide A-1: 41.7% by mass, (B) semi-aromatic polyamide B-1: 10.4% by mass, and (D) Polymer D-1: Pellets of polyamide composition P-3b were obtained in the same manner as in Example 1, except that the polymer was changed to 6.5% by mass.

[Comparative Example 4] Production of polyamide composition P-4b The blending amount was (A) aliphatic polyamide A-1: 41.7% by mass, (B) semi-aromatic polyamide B-1: 10.4% by mass, and (D) Polymer D-2: Pellets of polyamide composition P-4b were obtained in the same manner as in Example 1, except that the polymer was changed to 6.5% by mass.

[Comparative Example 5] Production of polyamide composition P-5b The blending amount was (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, and (D') Polymer D'-1: Pellets of polyamide composition P-5b were obtained in the same manner as in Example 1, except that the content was changed to 5.0% by mass.

[Comparative Example 6] Production of polyamide composition P-6b The blending amount was (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, and (D') Polymer D'-2: Pellets of polyamide composition P-6b were obtained in the same manner as in Example 1, except that the content was changed to 5.0% by mass.

[Comparative Example 7] Production of polyamide composition P-7b The blending amount is (A) aliphatic polyamide A-1: 24.3% by mass, (B) semi-aromatic polyamide B-1: 16.3% by mass, ( C) Phosphinates C-1: 9.0% by mass, and (D) Polymer D-1: 0% by mass using the same method as in Example 1, polyamide composition P-7b A pellet was obtained.

[Comparative Example 8] Production of polyamide composition P-8b The blending amount is (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, ( C′) Flame retardant C′-1 other than phosphinates: 16.0% by mass, and (D) Polymer D-2: 5.0% by mass Using the same method as in Example 1 , to obtain pellets of polyamide composition P-8b.

[Comparative Example 9] Production of polyamide composition P-9b The blending amount is (A) aliphatic polyamide A-1: 42.8% by mass, (B) semi-aromatic polyamide B-1: 10.8% by mass, ( C′) Flame retardant C′-2 other than phosphinates: 16.0% by mass, and (D) Polymer D-2: 5.0% by mass Using the same method as in Example 1 , to obtain pellets of the polyamide composition P-9b.

Using the obtained pellets of each polyamide composition, a molded product was produced by the above method, and various physical properties were measured and evaluated. Evaluation results are shown in Tables 1 to 5 below.

From Tables 1-3, including (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) phosphinates, and (D) polymer, (D ) Polyamide compositions P-1a to P-21a (Examples 1 to 21) in which the content of the polymer is in the range of 0.1% by mass to 8.0% by mass or less The molded articles obtained are flame retardant It was excellent in tensile strength, flexural modulus at the time of water absorption, and long-term heat resistance.
Also, in polyamide compositions P-3a, P-6a, P-9a and P-10a (Examples 3, 6, 9 and 10) containing different types of (D) polymers, D-1, D-2 and D-3 containing polyamide compositions P-3a, P-6a and P-9a (Examples 3, 6 and 9) were obtained from polyamide compositions P-10a containing D-4 The tensile strength and long-term heat resistance were particularly better than those obtained from (Example 10).
Also, in polyamide compositions P-2a and P-11a (Examples 2 and 11) and P-7a and P-12a (Examples 7 and 12) containing different types of (B) semi-aromatic polyamides , The molded articles obtained from polyamide compositions P-2a and P-7a containing B-1 (Examples 2 and 7) were obtained from polyamide compositions containing B-2 (Examples 11 and 12). The tensile strength and flexural modulus at the time of water absorption were particularly better than those of the molded article obtained from this method.
Also, in polyamide compositions P-2a and P-13a (Examples 2 and 13) and P-7a and P-14a (Examples 7 and 14) containing different types of (A) aliphatic polyamides, Molded articles obtained from polyamide compositions P-2a and P-7a containing A-1 (Examples 2 and 7) were obtained from polyamide compositions P-13a and P-14a containing A-2 (Example The tensile strength and flexural modulus at the time of water absorption were particularly better than the moldings obtained from 13 and 14).
Further, in the polyamide compositions P-8a and P-20a (Examples 8 and 20) containing different types of (C) phosphinates, the polyamide composition P-8a containing C-1 (Example 8) The molded article obtained from was particularly superior in tensile strength and flexural modulus upon water absorption than the molded article obtained from the polyamide composition P-20a containing C-2 (Example 20).

On the other hand, from Tables 4 and 5, the molded articles obtained from polyamide compositions P-1b, P-2b and P-7b (Comparative Examples 1, 2 and 7) containing no (D) polymer are difficult to It was inferior in flame resistance, bending elastic modulus at the time of water absorption, and long-term heat resistance.
Further, the content of the (D) polymer relative to the total mass of the components (A) to (D) is more than 8.0% by mass from the polyamide compositions P-3b and P-4b (Comparative Examples 3 and 4). The resulting molded article was inferior in flame retardancy and tracking resistance.
In addition, the content of the polymer (D') with respect to the total mass of the components (A) to (D') is 0.1% by mass or more and 8.0% by mass or less, but the oxygen index is less than 27%, and the main The molded article obtained from the polyamide composition P-5b (Comparative Example 5) containing the (D') polymer having no aromatic group in the chain had poor flame retardancy.
Further, the content of the polymer (D') relative to the total mass of the components (A) to (D') is 0.1% by mass or more and 8.0% by mass or less, but does not have an aromatic group in the main chain The molded article obtained from the polyamide composition P-6b (Comparative Example 6) containing the (D') polymer was inferior in flexural modulus upon absorption of water, long-term heat resistance and tracking resistance.
Further, instead of (C) phosphinates, a polyamide composition P-8b containing a nitrogen-based flame retardant C'-1 as a flame retardant that does not contain a halogen element other than (C') phosphinates (Comparative Example 8) and the polyamide composition P-9b (Comparative Example 9) containing a nitrogen and phosphorus-based flame retardant C'-2 is inferior in flame retardancy, tensile strength and flexural modulus upon water absorption. The molded article obtained from the polyamide composition P-9b (Comparative Example 9) was also inferior in tracking resistance.

From the above, according to the polyamide composition of the present embodiment, it is clear that a molded article that does not contain halogen and is excellent in flame retardancy, tensile strength, flexural modulus when absorbing water, and long-term heat resistance can be obtained. rice field.

According to the polyamide composition of the present embodiment, a molded article having excellent flame retardancy and excellent long-term heat resistance can be obtained in spite of containing no halogen. The molded article of this embodiment can be suitably used in the fields of automobiles, electrics and electronics, machinery and industry, office equipment, aviation and space.

Claims (13)

(A) an aliphatic polyamide;
(B) a semi-aromatic polyamide containing diamine units and dicarboxylic acid units;
(C) at least one phosphinate selected from the group consisting of a phosphinate represented by the following general formula (1), a diphosphinate represented by the following general formula (2), and condensates thereof; ,
(D) a polymer having an oxygen index of 27% or more and having an aromatic group in its main chain;
A polyamide composition containing
The (B) semi-aromatic polyamide contains 50 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (B) semi-aromatic polyamide,
The content of the (D) polymer is 0.1% by mass with respect to the total mass of the (A) aliphatic polyamide, the (B) semi-aromatic polyamide, the (C) phosphinates and the (D) polymer A polyamide composition having a content of 8% by mass or more.

(In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M ⁿ¹¹⁺ is an n11-valent metal ion. M is calcium or aluminum , n11 is 2 or 3. When n11 is 2 or 3, a plurality of R ¹¹ and R ¹² may be the same or different.
In general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M′ ^m21+ is an m21 valent metal ion. M' is calcium or aluminum . n21 is an integer of 1 or more and 3 or less. When n21 is 2 or 3, multiple R ²¹ , R ²² and Y ²¹ may be the same or different. m21 is 2 or 3; x is 1 or 2; When x is 2, multiple M' may be the same or different. n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x. ) 2. The polyamide composition according to claim 1, wherein the (D) polymer is polyphenylene sulfide, polyphenylene ether or maleic anhydride-modified polyphenylene ether. 3. The polyamide composition according to claim 1, wherein the (A) aliphatic polyamide contains diamine units and dicarboxylic acid units. The polyamide composition according to any one of claims 1 to 3, wherein the (A) aliphatic polyamide is polyamide 66. The content of the (C) phosphinates is 0 with respect to the total mass of the (A) aliphatic polyamide, the (B) semi-aromatic polyamide, the (C) phosphinates and the (D) polymer The polyamide composition according to any one of claims 1 to 4, which is .1% by mass or more and 30% by mass or less. The polyamide composition according to any one of claims 1 to 5, wherein the polyamide composition has a tanδ peak temperature of 90°C or higher. Any one of claims 1 to 6, wherein the content of (B) the semi-aromatic polyamide in the polyamide composition is 5% by mass or more and 50% by mass or less with respect to the total mass of the polyamide in the polyamide composition. or the polyamide composition according to claim 1. 8. The semi-aromatic polyamide (B) according to any one of claims 1 to 7, wherein the isophthalic acid unit is contained in an amount of 75 mol% or more in all dicarboxylic acid units constituting the semi-aromatic polyamide (B). of the polyamide composition. The semi-aromatic polyamide (B) contains 100 mol% of isophthalic acid units in all dicarboxylic acid units constituting the semi-aromatic polyamide (B), according to any one of claims 1 to 8. Polyamide composition. The polyamide composition according to any one of claims 1 to 9, wherein the polyamide composition has a weight average molecular weight of 10,000 or more and 50,000 or less. Polyamide composition according to any one of the preceding claims, further comprising at least one (E) filler. A molded article obtained by molding the polyamide composition according to any one of claims 1 to 11. A method for producing the polyamide composition according to any one of claims 1 to 11,
A method for producing a polyamide composition, comprising melt-kneading raw material components containing the (A) aliphatic polyamide, the (B) semi-aromatic polyamide, the (C) phosphinate and the (D) polymer.